1. Field of the Invention
The invention generally relates to a method of controlling process variables during PECVD deposition of a silicon-containing thin film. One important functional result of the variable control is avoidance of the uncontrolled deposition silicon-containing reactant species in the form of a film which creates a haze on a substrate.
2. Brief Description of the Background Art
Current interest in thin film transistor (TFT) arrays is particularly high because these devices are used in liquid crystal active matrix displays (LCDs) of the kind often employed for computer and television flat panels. The liquid crystal active matrix displays may also contain light-emitting diodes (LEDs) for back lighting. As an alternative to LCD displays, organic light-emitting diodes (OLEDs) have also been used for active matrix displays, and these organic light-emitting diodes require TFTs for addressing the activity of the displays.
The thin films deposited to form the TFT arrays are typically deposited upon a substrate using a plasma enhanced chemical vapor deposition (PECVD) process. PECVD is generally accomplished by introducing a precursor gas or gas mixture into a vacuum chamber that contains the substrate. The precursor gas or gas mixture is typically directed downwardly through a distribution plate situated adjacent to a substrate on which a film is to be deposited. The precursor gas or gas mixture in the chamber is energized (e.g., excited) into a plasma by applying energy to the gas mixture. One commonly used method of energy application (by way of example and not by way of limitation) is the introduction of radio frequency (RF) power into the chamber from one or more RF sources coupled to the chamber. The excited gas or gas mixture reacts to form a layer of material on a surface of the substrate that is positioned on a temperature controlled substrate support. Volatile by-products produced during the reaction are pumped from the chamber through an exhaust system.
The materials which form TFT arrays are typically deposited on a flat substrate using plasma enhanced chemical vapor deposition (PECVD). The substrate may be a semiconductor substrate, but more often is a transparent substrate, such as a glass, quartz, sapphire, or a clear plastic film. TFT arrays typically employ silicon-containing films, and, in particular, silicon nitride-containing films are often used for dielectric layers. A first silicon nitride-comprising film is referred to as the gate dielectric because it overlies the conductive gate electrode. A second silicon nitride-comprising film is referred to as the passivation dielectric and overlies the upper surface of a second conductive electrode, to electrically isolate the second conductive electrode from the ambient surrounding the upper surface of the TFT device.
There are a number of TFT structures which may employ silicon nitride gate insulators, and several of these are presented in a disclosure entitled “A Study on Laser Annealed Polycrystalline Silicon Thin Film Transistors (TFTs) with SiNx Gate Insulator”, by Dr. Lee Kyung-ha (Kyung Hee University, 1998). This disclosure is available at http://tftcd.khu.ac.kr/research/polySi. Dr. Lee Kyung-ha's disclosure pertains mainly to the use of laser annealed poly-Si TFTs, which is not the subject matter of the present invention, but the TFT structures are of interest as background material. The structures of interest are presented in Chapter 2 of the disclosure.
D. B. Thomasson et al., in an article entitled: “High Mobility Tri-Layer a-Si:H Thin Film Transistors with Ultra-Thin Active Layer” (1977 Society for Information Display International Symposium Digest of Technical Papers, volume 28, pages 176-179), describe active matrix liquid crystal displays where the TFT has an active layer thickness of about 13 nm. The TFT structure is a glass substrate with a molybdenum bottom electrode, a silicon nitride gate dielectric layer, an a-Si:H layer overlying the silicon nitride gate dielectric layer, n+ μc-Si:H doped source and drain regions, separated by a silicon nitride dielectric mesa, and with an aluminum contact layer overlying each source and drain region. This is referred to as a Tri-layer a-Si:H TFT structure. The authors claim that such hydrogenated amorphous silicon thin-film transistors with active layer thickness of 13 nm perform better for display applications than devices with thicker (50 nm) active layers. The linear (VDS=0.1V) and saturation region mobility of a 5 μm channel length device is said to increase from 0.4 cm2/V·sec and 0.7 cm2/V·sec, for a 50 nm a-Si:H device, to 0.7 cm2/V·sec and 1.2 cm2/V·sec, for a 13 nm a-Si:H layer device fabricated with otherwise identical geometry and processing. The gate dielectric silicon nitride was deposited from a reactant gas mixture of SiH4, NH3, and Ar at 100 mW/cm2, −150 V, 0.5 Torr, and 300° C. The passivation silicon nitride dielectric layer was deposited at the same conditions as the gate dielectric, with the exception of the substrate temperature, which was 250° C.
Young-Bae Park et al., in an article entitled: “Bulk and interface properties of low-temperature silicon nitride films deposited by remote plasma enhanced chemical vapor deposition” (Journal of Materials Science: Materials in Electronics 23 (2001), pp. 515-522), describe problems which occur when a gate dielectric, rather than being SiNx, is a hydrogenated silicon nitride film (a-SiNx:H). PECVD a-SiNx:H thin films are said to be widely used as a gate dielectric for a-Si:H TFT applications, due to the good interfacial property between an a-Si:H layer and an a-Si:Nx:H layer. However, the a-Si:H TFTs with SiNx:H gate dielectric are said to have instability problems, such as the threshold voltage shift and the inverse subthreshold slope under a DC gate voltage bias. These instability problems are said to be caused by the high trap density in the SiNx:H film and the defects created at the a-Si:H/SiNx:H interface. Charge trapping in the SiNx:H is said to be from the electron injection under an applied field and due to the localized states of the Si dangling bonds, Si—H and N—H bonds in the forbidden gap. The authors claim that PECVD SiNx:H dielectric films are not useful as a gate insulator because they contain large amounts of bonded hydrogen (20%-40%) in the form of N—H and Si—H bonds.
The authors propose that a remote plasma enhanced chemical vapor deposition of the gate dielectric layer be carried out. The NH3 precursor is excited in a remote plasma zone (at the top of the chamber) to produce NH* or NH2*+H*, after which the activated species* from the plasma zone react with SiH4 introduced downstream through a gas dispersal ring to form the SiNx:H electrical insulator with a reduction in the amounts of bonded hydrogen in the form of Si—H bonds, which are said to easily lose hydrogen to form a dangling bond of the kind known to reduce performance of the TFT device over time.
A presentation entitled: “Low Temperature a-Si:H TFT on Plastic Films: Materials and Fabrication Aspects”, by Andrei Sazonov et al. (Proc. 23rd International Conference on Microelectronics (MIEL 2002), Vol. 2, NIS, Yugoslavia, 12-15 May 2002), related to fabrication technology for a-SiH thin film transistors at 120° C. for active matrix OLED displays on flexible plastic substrates. The TFTs produced were said to demonstrate performance very close to those fabricated at 260° C. The authors claim that, with the proper pixel integration, amorphous hydrogenated silicon (a-Si:H) TFTs are capable of supplying sufficiently high current to achieve required display brightness and thus can be a cost-effective solution for active matrix OLED displays.
The silicon nitride films used to produce the fabricated TFT samples were amorphous silicon nitride deposited at 120° C. by PECVD from SiH4 and NH3 gaseous precursors. The film is said to have a lower mass density and higher hydrogen concentration in comparison with films fabricated at 260° C. to 320° C. In the study, a series of a-SiNx:H films with [N]/[Si] ratio ranging from 1.4 to 1.7 were deposited (at 120° C.). The hydrogen content in the films was in the range of 25-40 atomic percent. Generally, the films with higher [N]/[Si] are said to have higher mass density and higher compressive stress. The resistivity of a-SiNx:H films estimated at the field of 1 MV/cm was said to be in the range of 1014-1016 Ohm·cm, and the films with higher [N]/[Si] were said to have a higher breakdown field and dielectric constant than their lower N-content counterparts. A table of data supporting these conclusions was presented as part of the presentation.
Compared to their higher temperature counterparts, the lower temperature a-SiNx films are characterized by higher hydrogen content. The nitrogen-rich films with a hydrogen concentration of about 40% or more exhibit hydrogen bonded predominantly to nitrogen atoms, with a high [N]/[Si] ratio achieved solely due to the high concentration of N—H bonds. The TFTs produced an a plastic film substrate at lower temperatures require a higher threshold voltage (4-5 V) than the TFTs produced on glass at the higher temperatures. As a result, the ON current observed for TFTs produced at the lower temperatures is lower. Although the performance properties of these TFTs complies with the requirements for OLED applications, it is apparent that it would be beneficial to lower the threshold voltage of the TFTs produced at the 120° C. temperature.
As indicated above, the performance capabilities of the TFT are a direct result of the structural characteristics of the films formed during fabrication of the TFTs. The structural characteristics of the films depend directly upon the process conditions and relative amounts of precursors which are used during formation of the films which make up the TFTs. As the size of flat panel displays increase, it becomes increasingly difficult to control the uniformity of the individual films produced across the increased surface area. With respect to PECVD deposited silicon-nitride comprising films, which are used either as the gate dielectric layer or as the passivation dielectric layer, control of uniformity of the film across the substrate becomes increasingly important when the PECVD is carried out in a process chamber having parallel-plate capacitively-coupled electrodes over about two meters by two meters.
The disclosure above is related to the deposition of silicon nitride films to form TFT structures. This is to emphasize how a change in film deposition variables has a major effect on the electrical characteristics and performance of the device which includes the deposited film. However, the present invention is not intended to be limited to instances where a silicon nitride film is deposited, but is also applicable in instances where polycrystalline silicon (polysilicon), microcrystalline silicon (μc-Si), amorphous silicon (α-silicon), and silicon oxide films are deposited, by way of example and not by way of limitation.
The flat substrates upon which large TFT display devices are created frequently comprises a material that is essentially optically transparent in the visible spectrum, as discussed above. The substrate may be of varying shapes or dimensions. Typically, for TFT applications, the substrate is a glass substrate with a surface area greater than about 40,000 cm2.
Another device which employs the use of silicon-containing films and which is also typically created on a large substrate surface is a solar cell. Solar cells may be fabricated using techniques which are similar to those described above, where silicon-containing films are deposited using PECVD deposition techniques. The substrates for solar cells typically exhibit a surface area in the range of about 40,000 cm2 to about 60,000 cm2.
During recent process development by the current inventors with respect to large TFT display screens, there were instances where a haze was observed on the transparent substrate during processing; particularly during processing which involved the deposition of silicon-containing films. It was subsequently determined that the TFT device performance was affected by the processing conditions which produced the haze. With respect to OLED devices, a silicon-containing passivation layer which exhibits a haze produces a fuzzy, less desirable image.
Prior to the present invention, there was a need to determine the cause of the haze, which was an indication of unacceptable process conditions during the PECVD deposition of silicon-containing films on large substrate surfaces (where the substrate surface area was larger than about 25,000 cm2).